EP1353882A1 - Method for rendering surfaces resistant to soiling - Google Patents

Method for rendering surfaces resistant to soiling

Info

Publication number
EP1353882A1
EP1353882A1 EP20020702249 EP02702249A EP1353882A1 EP 1353882 A1 EP1353882 A1 EP 1353882A1 EP 20020702249 EP20020702249 EP 20020702249 EP 02702249 A EP02702249 A EP 02702249A EP 1353882 A1 EP1353882 A1 EP 1353882A1
Authority
EP
Grant status
Application
Patent type
Prior art keywords
surfaces
repellent
dirt
according
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20020702249
Other languages
German (de)
French (fr)
Inventor
Thomas Frechen
Stephan Hüffer
Ekkehard Jahns
Harald Keller
Christian Lach
Elmar STÖCKELMANN
Yi Thomann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/42Coatings comprising at least one inhomogeneous layer consisting of particles only

Abstract

The invention relates to a method for rendering surfaces resistant to soiling. The method is characterized in that the surfaces are coated with particles, which have an average diameter ranging from 3 nm to 5 νm and which are comprised of a material that has a surface energy of at least 20 mN/m.

Description

A method for soil-repellent finishing of surfaces

description

The present invention relates to a method for soil-repellent treatment of surfaces, characterized in that coating the surface with particles having an average diameter of 3 nm to 5 microns and consist of a Mate rial, which has a surface energy of at least 20 mN / has m and is selected from organic polymers and Copo- lymeren and inorganic solid oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 of the Periodic Table.

Deposits and caking in apparatuses and apparatus parts for plant construction represent a serious problem in the industry, especially in the chemical industry. Apparatus, tank and reactor walls, vessel walls, discharge devices, valves, pumps, filters, supply are dense particularly affected, centrifuges, columns, dryers, centrifugal separators, scrubbers, comminution machines, internals, packing elements, heat exchangers, evaporators, condensers, nozzles, atomizers, spray dryers, crystallizers, filling and mixing elements. These deposits are referred to as coverings or as fouling.

The coverings can act in a variety of damaging or hindering the process and lead to the need to shut down repeatedly corresponding reactors or processing machines and clean.

With pads encrusted measuring devices can be erroneous and cause misleading results may occur due to the incorrect operation.

In other applications coverings are disadvantageous. After wetting and evaporation of water leaves a residue on surfaces, for example, rain water on windows, motor vehicles, road signs or billboards. Flowing fluids through the wetting cause friction at the incident flow sur- faces. This results for example in ships, but also for liquids flowing through pipelines to friction losses.

By wetting liquids may, for example, emulsions, suspensions, polymer dispersions, films and deposits in the interior of process equipment, such as pipes, boilers, tanks, reactors, heat exchangers, evaporators, condensers, pumps, nozzles, atomizers, spray rockers, crystallizers or bottling plants and laboratory equipment cause.

Electrical devices and components in weathered and unweathered, but in communication with the ambient air areas, pollute on their surfaces. By pollution itself, and especially by wetting the contamination for example by rain, fog or humidity, the surfaces are electrically conductive to some extent, whereby creepage currents occur which may affect the function of the components. Next there is for example in high-voltage transmission lines and voltage conversion devices to substantial energy losses due to the contamination of the insulators. Furthermore, the pollution is directions cause of corrosion of the construction projects and the substrate for additional biological contamination by microorganisms, for example, algae, lichens, mosses or mussels.

By wetting (humidification) unwanted living organisms, for example microorganisms, biofilms, algae, lichens, mosses or shellfish can grow on surfaces such as roofs, walls, shower stalls, vessels or heat exchangers.

By wetting remain partially attached to the inner surface of the packaging materials and materials containing liquids, such as Me, honey, yogurt or toothpaste liquid. This can not be used a part of the packaged product, if you do not want complicated cleaning it. Furthermore, the recycling of packaging materials is difficult because of contamination by the packaged. Finally, the Fester this perishable leftovers is also a hygienic problem and leads, particularly in the summer to unpleasant odors near garbage cans.

When solid surfaces come into contact with particles, adhesion occurs. The adhesion of particles such as dirt, dust, soot, industrial powder, pollen, spores, bacteria or viruses leads to contamination of the surfaces and is undesirable in many cases.

Another problem that arises from the formation of deposits is due to the fact that in particular the molecular parameters such as molecular weight or degree of crosslinking differ in deposits in polymerization reactors significantly from the product specifications. If deposits loosen during operation, they may contaminate the product (eg specks in paints, inclusions in suspension beads). can struggled ablative undesirable in the case of reactor, packing elements or mixing elements, continues to lead to an undesirable change in the residence of the apparatus or impair the effectiveness of the internals or mixing elements as such. Abbre--reaching coarse parts of toppings can trags- for plugging off and cause processing devices, while small parts can lead to impairment of the product produced.

The deposits whose formation is to be prevented, Han delt it is coverings, which may be caused for example by reactions with or on surfaces. Other reasons are adhesion to surfaces that may be caused by van der Waals forces, polarization effects or electrostatic double layers. Other important effects are stagnation of the motion at the surface and, optionally, reactions in said stagnating layers. Finally, include: precipitation from solutions, evaporation residues, cracking on locally hot surfaces and microbiological activities.

The causes are dependent on the particular material combinations and can be effective alone or in combination. During the operations, for which the undesirable deposits are formed, are fairly well studied (eg AP Watkinson and DI Wilson, Experi ental Thermal Fluid Sci. 1997, 14, 361 and references cited therein), there is little common concepts for the prevention of the above deposits described. The previously known methods have disadvantages.

Mechanical solutions have the disadvantage that they can cause significant additional costs. Additional reactor internals may continue to significantly change the flow profile of fluids in the reactors and thus require an expensive redevelopment of the process. Chemical additives can lead to undesired contamination of the product; some additives pollute the environment.

For these reasons, it is increasingly looking for ways to reduce the fouling tendency by modification of apparatuses and apparatus parts for chemical plant directly.

From EP-A 0,745,568 it is known that surfaces can be made water-repellent by fluorinated and especially perfluorinated alkylsilanes. However, these substances are comparatively expensive. WO 00/40775, WO 00/40774 and WO 00/40773 describe methods for coating of surfaces, particularly surfaces of reactors for the high pressure polymerization of 1-olefins or surfaces of heat exchangers, by electroless plating of a NiP / poly 5 tetrafluoroethylene-layer or a CuP / polytetrafluoroethylene layer, through which the respective metal surfaces anti-adherent can be modified. When using the coated surfaces by the process described in apparatuses and apparatus parts for chemical plant construction, in particular reactors for

10, the high-pressure polymerization of 1-olefins is observed, however, that the surfaces are not sufficiently mechanically stable, so that caking of the product can be observed after a longer application again. possible re-coating of a partially ablated NiP / polytetrafluoroethylene layer

15 is not. Furthermore, it can be observed that, once deposited NiP / polytetrafluoroethylene layer can only be poorly removed when it is no longer desired in a reactor or apparatus part. In particular, in reactors with a rapid change of product, in which occasional responses in about

20 400 ° C are to be performed, a coating with NiP / polytetrafluoroethylene has not proved successful. Finally, it is to be mentioned as a drawback that in particular large quantities must be used in immersion baths in coating large-volu strength reactors, leading to substantial solvent waste.

25

WO 96/04123 discloses self-cleaning surfaces which can be coated with poly-tetrafluoroethylene, and have particularly hydrophobic properties. The structuring is achieved by etching or embossing the surface, by physical methods

30 such as sand blasting or ion etching with, for example oxygen. The distance of the elevations or depressions is more than 5 microns. Subsequently, the surface is coated with Teflon. However, the mechanical stability of coats hydrophobicized is far too low for use in chemical engineering

35 construction, in particular for polymerization reactors in which strong shear forces act. However, the so-applied layers are not transparent enough for many applications.

Furthermore, textured surfaces with hydrophobic properties 40 are properties (EP-A 0933388), which are manufactured so that it etches the surface in question, for example, thereby producing elevations or grooves at a distance of less than 10 microns on the surface, and then with a layer of a hydrophobic polymer, such as polyvinylidene fluoride, exceed 45 pulls, wherein the surface energy of the corresponding material is less than 20 mN / m. These layers may further fluorinated waxes, for example, contain Hostaflone®. The thus modified surfaces are hydrophobic and oleophobic. As applications holders of wafers in semiconductor production called to continue the production or coating of headlamps, windscreens or covers of solar cells. A disadvantage of the method, however, is that the structure after partial mechanical degradation is difficult to renew.

From DE 198 60 139 Cl a process for producing an ultraphobic surface is known to be coated at the surfaces produced by a method selected Ni (OH) which is subsequently rendered hydrophobic. As a bonding agent, the use of precious metal layers such as Ag, Pt and Au in particular is recommended. However, the disclosed process is expensive and relatively complicated.

Finally, in DE-A 100 22 246 (published on ...) loading a coating agent is known which contains a finely divided powder and a binder. For application of a binder, a solvent is always necessary, which is undesirable in many cases.

It was therefore the task

provide a method for soil-repellent finishing of surfaces, which avoids the aforementioned disadvantages in the prior art and it does not contain a binder to provide dirt-repellent surfaces and to provide uses for articles with dirt-repellent surfaces.

It has now been found that this object can be achieved by coating the stain resistant be equipped surface with particles having an average diameter of 3 nm to 5 microns and consist of a material which energy a surface of at least 20 mN / m Has.

The inventive method consists of several steps.

In the first step prepares the dirt-repellent surface auszurüstende by making them sticky before the coating step, so that the present invention particles to be applied are fixed. This can be done by several alternative steps:

One may apply a so-called primer which performs the function of an adhesive. Suitable primers are, for example polymer dispersions, such as ethylene / acrylic acid copolymers that are neutralized with ammonia or amines eil particle; particularly preferred example is Lugalvan DC® BASF AG; Acronal® V or 210 as a particularly preferred example of an adhesive. Furthermore, hot-melt adhesive, and infusible polymers such as polyethylene, polypropylene, polystyrene, polyvinyl chloride or polyoctadecyl vinyl ether are suitable. Furthermore, waxes such as poly- ethylene waxes, polypropylene waxes, Carnaύbawachse, montan waxes or paraffin waxes suitable as primers. The thickness of the applied adhesive layer is for the inventive procedural not critical and can be from 0.1 microns to 10 mm.

Alternatively, in cases in which the dirt-repellent auszurüstende surface is made of plastics, they are heated for a short time to a temperature which is above the glass transition temperature of the respective plastic or be partially solubilized or swollen with a solvent.

Then coated to the dirt-repellent surfaces to be equipped with particles having an average diameter of 3 nm to 5 microns and consisting of a material having a surface energy of at least 20 mN / m. The particles to be applied are characterized by their hydrophobic surface, its porous structure and its mean diameter.

The porous structure can be best described by the BET surface area, measured according to DIN 66131.. The particles used have a BET surface area in the range of 5 to 1000 m 2 / g, preferably from 10 to 800 m 2 / g and particularly preferably from 20 to 500 m 2 / g.

The particles consist of a material which has a surface energy of 20 mN / m or more. Suitable materials are organic polymers such as polyethylene, polypropylene, butylene polyisobutylene and polystyrene and also copolymers thereof with each other or with one or more other olefins, such as styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-Ethylhexylmeth - acrylate, maleic anhydride or N-methyl. A preferred polyethylene or polypropylene is described for example in EP-A 0 761 696th

Other suitable materials include solid inorganic oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 of the Periodic Table of the Elements, e.g., calcium oxide, silicon dioxide or aluminum oxide, calcium carbonate, Calciumsulf t or calcium silicate, with alumina and silica are preferred. Particularly preferred silicon dioxide is in its modifica- tion as silica gel. Very particular preference fumed silica, which are available for example as Aerosil® trademarks of firm Degussa-Huls commercially are. The solid inorganic oxides may Trains t thermally by heating to 400 to 800 ° C and are rendered hydrophobic by PREFERRED physisorbed or chemisorbed organic or organometallic compounds. By exposing the particles before the coating step with organometallic compounds to that contain at least one functional group, for example alkyl lithium compounds such as methyllithium, n-butyllithium or n-hexyllithium; or silanes such as hexamethyldisilazane, Octyltrimethoxysilane, trimethylchlorosilane or dichlorodimethylsilane.

The average diameter of the particles is in the range of 3 nm to 5 microns, preferably from 5 nm to 1 micron, and most preferably in the range of 7 nm to 0.5 microns.

If desired, the dirt-tight surfaces to be equipped with mixtures of particles of two or more various materials can be coated.

The mixing ratios are selected within wide ranges, but it must be ensured that the particles that of material having a surface energy of more than 20 mN / m, are present to more than 50 wt .-% of the particles preferably, greater than 75 weight .-%.

The particles described above are applied to the stain resistant auszurüstende surface. This application is also known as coating. The coating is carried out without liquid dispersant. In one embodiment of the inventive method a workpiece to be coated with the above-described particles is pollinated. This method is particularly suitable for flat surfaces such as films.

In another embodiment of the present invention, which is particularly suitable for interior surfaces of equipment or vessels, filling the apparatus or the container totally or partially with the particles ensures a sufficient convection and then removes the non-fixed particles.

The coating step can be repeated one, if desired.

By the inventive method, the dirt-repellent surfaces are coated to be equipped with a particle layer, whose thickness is in the range of 3 nm to 10 microns. Preferably designate the thickness, not greater than 1 micron. Particularly preferably, the thickness of the particle layer is in the range of 5 nm to 0.3 microns.

After coating, the layer is allowed to age before the overall 5 are used genstände with the inventively coated surfaces. This aging can take 20 minutes to about 10 hours, preferably 1 to 3 hours. The aging can be performed at room temperature or at slightly elevated temperature; but the temperature should be high enough so that particles 10 or primer begin to sinter. It has been found that a temperature in the range of 20 to 50 ° C in many cases is sufficient.

The selection of the materials of the dirt-repellent surfaces 15 to be equipped is not critical. Suitable are for example polymers such as polyethylene, polypropylene, polystyrene, polyester, Plexiglas, polyamides, polycarbonates or polyurethanes, further metals and alloys such as silver, palladium, platinum, steel, copper, nickel, as well as paper, cardboard, textiles, stone, ceramic, Be - 20 ton, porcelain, glass or wood. Particularly useful are transparent materials such as glass, Plexiglas and polycarbonates Makrolon® brands.

Another object of the present invention are soil-repellent finished surfaces of the above-described 25 methods. They can be cleaned by simply rinsing with water, for example, extremely easy; unlike described in the prior art surfaces no addition of surfactants is necessary. Furthermore, surface-to the invention are highly transparent 30 chen.

The surfaces have been found to be especially soil-repellent to the following media: water, coffee, honey, glycerol rin, 32 wt .-% aqueous hydrochloric acid, 5 wt .-% aqueous sodium hydroxide solution, 35 wt .-% 30 aqueous solution of polyacrylic acid, 30 wt .-% aqueous solution of a copolymer consisting of vinyl pyrrolidone and vinyl - imidazole, aqueous polymer dispersion Acronal® 290 D (BASF AG), aqueous polymer dispersion Styronal® D 808 (BASF AG).

40 Another object of the present invention are tubes or pipes with surfaces which are equipped dirt-repellent according to the method described above. They are particularly suitable for pumping through solutions because no ablative because of the dirt-repellent surfaces finished

form wrestled 45 and therefore the flow resis and remains low. Particularly preferred are pipes made of glass, plexiglass or o α. ω

H α.

- *

O

do not let wet water and are protected in this way particularly long from rotting.

Another object of the present invention relates to textile and leather tilgewebe whose surface is refined by the inventive method. They are particularly water- and stain-resistant. Due to the high transparency of the inventively coated surfaces it is also achieved that colors and prints to their best advantage.

Another object of the present invention are filter materials and separation membranes, for example, the chlor-alkali electrolysis according to the invention with surfaces finished.

Another object of the present invention are papers, cardboard and cardboard according to the invention with surfaces finished. They prevent soaking wet and reduce pollution. As a special case of papers notes and official documents are to be mentioned, the inventive method is suitable for the coating in particular. Due to the high transparency of the inventively coated surfaces it is also achieved that colors and prints to their best advantage.

working examples

example 1

A glass plate was coated with a doctor blade with a knife gap of 50 microns with an aqueous dispersion of a copolymer consisting of ethylene and acrylic acid (Lugalvan® DC, BASF AG), and 15 min drying in room air.

Then, the coated side of the glass plate with a powder was dusted consisting coverage of a hydrophobic Siliziumdioxidpigment having a BET surface area of 220 m 2 / g (DIN 66131), by the particles were spread through a sieve over the surface, and 2 h at stored at -20 ° C. Subsequently the coated side was blown off with compressed air. an optical totally transparent layer showed no turbidity when watching in the back light was obtained.

Figure 1 shows a scanning electron micrograph of the film prepared according to the recordable. example 2

A glass plate was coated as described in Example 2. FIG. In contrast to Example 2, the glass plate was stored after the powder coating 2 h at 40 ° C. The coated glass plate was also optically transparent, and showed completely when viewing against the light no turbidity.

Comparative Example:

A glass plate was coated as described in Example 2. FIG. In contrast to Example 2, the glass plate was determined by the powder coating 2 h stored at 80 ° C. The coated glass plate was not visually completely transparent. It showed a slight haze when viewing against the light.

Tests of wettability:

The coated glass described in Examples 1 and 2 were panels mounted on a flat table and is inclined 2 ° from the horizontal. Then, in succession, the following fluids were applied in a defined amount and in the form of drops:

- water (30 mg)

Coffee (30 mg)

Honey (59 mg)

Glycerol (49 mg)

32 wt .-% aqueous hydrochloric acid (41 mg) - 5 wt .-% aqueous sodium hydroxide (45 mg)

30 wt .-% aqueous solution of polyacrylic acid (47 mg)

30 wt .-% aqueous solution of a copoly older, consisting of

Vinylpyrrolidone and vinylimidazole (35 mg) aqueous polymer dispersion Acronal 290 D (BASF AG, 58 mg) - aqueous polymer dispersion Styronal D 808 (BASF AG, 46 mg)

All liquids from pearled at an inclination angle of 2 ° from the coated glass plates from Examples 1 and 2, leaving behind no residue.

In a comparative experiment the liquids listed above were applied to a glass plate which had, but not only coated with the copolymer consisting of ethylene and acrylic acid with hydrophobic Siliziumdioxidpigment. The angle of inclination of the glass plate was also 2 ° to the horizontal. In all cases there was wetting; with the exception of water any liquid left residue on the glass plate.

The static contact angle of the coated glass plates from Examples 1 and 2 with respect to water is greater than 160 °.

Test the soil removal:

The coated glass plates of Examples 1 and 2 were treated with 100 mg / cm 2 carbon black powder (Printex V Degussa-Hüls AG, mean particle diameter of primary particles: 25 nm) spotted and then washed with water. Here, the carbon black powder is removed by the beading of water droplets, so that without the use of detergents, the original clean surface was obtained again.

Claims

Pa s t t rue before to sp
1. A method for soil-repellent finishing of surfaces, characterized in that coating the surface with particles having an average diameter of 3 nm to 5 microns and consist of a material which has and selecting a surface energy of at least 20 mN / m from organic polymers and copolymers, and solid inorganic oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 of the Periodic Table.
2. The method according to claim 1, characterized in that the particles ben an average diameter of 7 nm to 0.5 microns HA.
3. The method according to claims 1 or 2, characterized in that the particles have a porous structure.
4. The method according to claims 1 to 3, characterized in that one makes the surface sticky dirt repellent auszurüstende before coating.
5. The method according to claims 1 to 4, characterized gekennzeich- net that coating the stain resistant auszurüstende surface with a primer selected from adhesives, hot melt adhesives and polymer dispersions, and then coated with particles.
6. The method according to claims 1 to 4, characterized in that the dirt-repellent auszurüstende Kunststoffo- berfläche to a temperature above the glass transition temperature or heated with a solvent dissolves or swells and then coated with particles.
7. dirt repellent finished surfaces with high transparency, obtainable by the process according to claims 1 to. 6
8. tubes or pipes with dirt-repellent finish surfaces according to claim. 7
9. vessels and packages with dirt-repellent surfaces finished according to claim. 7
10. Not prone to icing or pollution motor vehicles with dirt-repellent surfaces finished according to claim. 7
11. Use of apparatuses or apparatus parts, particularly sight glasses, with dirt-repellent surfaces finished according to claim 7 in plants.
12. Sanitary, fittings, swimming pools, showers, catheters, and medical tubes with dirt-repellent surfaces finished according to claim. 7
13. wooden objects with dirt-repellent finish surfaces according to claim. 7
14. textile fabric and leather with stain-repellent finish surfaces according to claim. 7
15, filter materials and separation membranes with dirt repellent 'send equipped surfaces according to claim. 7
16. papers, cardboard and cardboard packaging with dirt-repellent finish surfaces according to claim. 7
EP20020702249 2001-01-12 2002-01-10 Method for rendering surfaces resistant to soiling Withdrawn EP1353882A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE10101162 2001-01-12
DE10101162 2001-01-12
PCT/EP2002/000166 WO2002055446A1 (en) 2001-01-12 2002-01-10 Method for rendering surfaces resistant to soiling

Publications (1)

Publication Number Publication Date
EP1353882A1 true true EP1353882A1 (en) 2003-10-22

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Country Status (4)

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US (1) US20040047997A1 (en)
EP (1) EP1353882A1 (en)
JP (1) JP2004525754A (en)
WO (1) WO2002055446A1 (en)

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